Thiono-phosphoric(phosphonic) acid ester formaldoximes

ABSTRACT

Thiono-phosphoric(phosphonic) acid ester formaldoximes of the general formula   in which R and R2 each is an alkyl radical with 1-6 carbon atoms, and R1 is an alkyl or alkoxy radical with 1-6 carbon atoms, WHICH POSSESS INSECTICIDAL, ACARICIDAL AND FUNGICIDAL PROPERTIES.

United States Patent [191 Hoffman et al.

[ NOV. 4, 1975 THl0N0-PHOSPHORIC(PHOSPHONIC) ACID ESTER FORMALDOXIMES [75] Inventors: Hellmut Hoffman,

Wuppertal-Elberfeld; Wolfgang Behrenz, Cologne-Stammheim; I Ingeborg Hammann, Cologne, all of Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen', Germany [22] Filed: Oct. 5, 1971 [21] Appl. No.: 186,815

[30] Foreign Application Priority Data OTHER PUBLICATIONS Fine Chemicals Patents Journal, 7, No. 21, German 5:2 (5-31-67).

Primary ExaminerRichard L. Raymond Attorney, Agent, or FirmBurgess, Dinklage & Sprung [57] ABSTRACT Thiono-phosphoric(phosphonic) acid ester formaldoximes of the general formula in which R and R each is an alkyl radical with 1-6 carbon atoms, and R is an alkyl or alkoxy radical with 1-6 carbon atoms,

which possess insecticidal, acaricidal and fungicidal properties.

7 Claims, No Drawings THlONO-PHOSPHORIC(PHOSPHONIC) ACID ESTER FORMALDOXIMES ducing such compounds and for using such compounds in a new way especially for combating pests, e.g. insects and acarids, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

it is known from German Published Specifications 1,238,902 and 1,009,181 that thionophosphoric acid (Illa) in which R and R each is an alkyl radicaliwith l-6 carbon 7 atoms, and R, is an alkyl or alkoxy radical with 1-6 carbon atoms. These new compounds have been found to exhibit strong insecticidal, acaricidal and fungicidal activity.

The present invention also provides a process for the preparation of a compound of the formula (1) above, in which a formaldoxime derivative of the general formula is reacted, in the form of an alkali metal, alkaline earth metal or ammonium salt thereof or in the presence of an acid-binding agent, with a thionophosphoric(phosphonic) acid ester halide of the general formula P-Hal (lll),

in which formulas v R, R and R have the meanings stated above, and Hal is a halogen atom, preferably a chlorine atom.

Surprisingly, the thionophosphoric(phosphonic) acid ester formaldoximes according to the invention possess a substantially better insecticidal and acaricidal activity than the known thionophosphoric acid ester benzaldoximes of analogous constitution and of the same directions of activity; moreover, they are also superior as regards activity to the known 0,0-dimethyl-S-(l,2-

dicarbethoxyethyl)-dithiophosphoric acid ester. The compounds according to the invention therefore represent a genuine enrichment of the art.

If 0,0-diethylthionophosphoric acid ester chloride and l-cyano-1-methylmercaptoformaldoxime are used as starting materials, the reaction course can be represented by the following equation:

acid-binding CN agent CN (C,H O) PON=C (IV) HCl SCH SCH,

(Ha) (I) Preferably, in formulas (I), (II) and (III), R, R, and R each is a lower alkyl radical with 14 carbon atoms, namely methyl, ethyl, nor isopropyl or n-, sec.-, tert.- or isobutyl, R alternatively being a lower alkoxy radical with 1-4 carbon atoms.

As examples of the thionophosphoric(phosphonic) acid ester halides which can be used, there are mentioned:

0,0-dimethy1-, 0,0-diethyl-, 0,0-dipropyl-, 0,0-diisopropyl-, O-methyl-O-ethyl-, O-methyl-O-isopropyl-, O-ethyl-O-isopropyl-, 0,0-dibutyl-, O-methyl-O-butyl and O-isopropy1-O-butyl-thionophosphoric acid ester chlorides; and

O-methyl-methane-, O-ethyl-propane- O-isopropylethane-, O-butyl-methane-, O-methyl-isopropane-,

. O-methyl-ethane-, O-ethyl-ethane-, O-propylmethane, O-butyl-ethane-, O-methyl-butane-, O-

ethyl-isopropane-, O-butyl-isopropane and O- butyl-butane-thionophosphonic acid ester chlorides.

The thionophosphoric(phosphonic) .acid ester halides are known, and can be prepared according to customary methods, as can the l-cyanoformaldoximes. The latter can, for example, be prepared from the reaction of alkylmercaptans and chloro-acetonitrile in the presence of alkali metal alcoholates, followed by oximation with ethylnitrite.

The process is preferably carried out with the use of suitable solvents or diluents. As such, practically all inert organic solvents are suitable, especially aliphatic and aromatic optionally chlorinated hydrocarbons, such as benzene, toluene, Xylenes, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; ethers, such as diethyl ether, dibutyl ether and dioxane; ketones, for example acetone and methylethyl, methyl-isopropyl and methylisobutyl ketones; and nitriles, such as acetonitrile and propionitrile.

As acid-binding agents, all customary acid-acceptors are suitable. Particularly good results have been ob- 3 tained with alkali metal carbonates and alcoholates, such as sodium and potassium carbonates, methylates and ethylates, as well as with aliphatic, aromatic and heterocyclic amines, for example triethylamine, dimethylamine, dimethylaniline, dimethylbenzylamine and pyridine.

The reaction temperature can be varied within a fairly wide range. In general the work is carried out at from about to 120C, preferably at from about 40 to 55C.

The reaction is, in general, carried out at normal pressure.

In the process, the starting materials are, in most cases, used in equimolar amounts; an excess of one or the other of the reactants brings no substantial advantages. The reaction is preferably carried out in the presence of one of the above-mentioned solvents and of an acid-acceptor, within the stated temperature range;

after several hours stirring, the reaction mixture is worked up by any usual method.

The substances according to the invention are obtained in most cases in the form of colorless or colored, viscous, water-insoluble oils, which cannot be distilled without decomposition but can, by so-called slight distillation, that is by prolonged heating at moderately elevated temperatures under reduced pressure, be freed from the last volatile components and in this way be purified.

For their characterization, their refractive indexes are especially useful.

As already mentioned, the new thionophosphoric (phosphonic) acid ester formaldoximes are characterized by an outstanding insecticidal and acaricidal effectiveness against crop pests, pests harmful to health and pests of stored products. They possess a good activity against both sucking and biting insects, and mites (Acarina), whereas they exhibit only a low phytotoxicity. They also possess fungicidal properties, especially against phytopathogenic soil fungi.

For these reasons, the compounds according to the invention may be used with succes as pesticides in crop protection and the protection of stored goods, as well as in the hygiene field.

To the sucking insects contemplated herein there belong, in the main, aphids (Aphidae) such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphum solanifolii), the currant gall aphid (Cryptomyzus korschelti), the rosy apple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterus arundim's) and the cherry-black-fly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiotus hederae) and the soft scale (Lecanium hesperidum) as well as the grape mealybug (Pseudococcus maritimus); thrips (Thysanoptera), such as Hercinothrips femoralis, and bugs, for example the beet bug (Piesma quadrata), the red cotton bug (Dysdercus intermedius), the bed bug (Cimex lectularius), the assassin bug (Rhodnius prolixus) and Chagas bug (Triatoma infestans) and, further, cicadas, such as Euscelis bilobatus and Nephotettix bipunctatus; and the like.

In the case of the biting insects contemplated herein, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plutella maculipennis), the gypsy moth (Lymantria dispar), the brown-tail moth (Euproctis chrysorrhoea) and tent caterpillar (Malacosoma neustria); further, the cabbage moth (Mamestra brassicae) and the cutworm (Agrotis sggetum), the large white butterfly (Pieris brassicae), the small winter moth (Cheimalobia brumata), the green oak tortrix moth (Tortrix viridana), the fall armyWOrmKLaphygma frugiperda) and cotton worm (Prodenia litura), the ermine moth (Hyponomeuta padella), the Mediterranean flour moth (Ephestia kiihniella) and greater wax moth (Galleria mellonella); and the like.

Also to be classed with the biting insects contemplated herein are beetles (Coleoptera), for example the granary weevil (Sitophilus granarius Calandra granaria), the Colorado beetle (Leptinotarsa decemlineata), the dock beetle (Gastrophysa viridula), the mustard beetle (Phaedon cochleariae), the blossom beetle (Meligethes aeneus), the raspberry beetle (Byturus tomentosus), the bean weevil (Bruchidius Acanthoscelides obtectus), the leather beetle (Dermestesfrischi), the khapra' beetle (Trogoderma granarium), the flour beetle (Tribolium castaneum), the northern corn billbug (Calandra or Sitophilus zeamais), the drugstore beetle (Stegobium paniceum), the yellow mealworm (Tenbrio molitor) and the saw-toothed grain beetle (Oryzaephilus surinamensis), and also species living in the soil, for example wireworms (Agriotes spec.) and larvae of the cockchafer (Melolontha melolontha); cockroaches, such as the German cockroach (Blattella germanica), American cockroach (Periplaneta americana), Madeira cockroach (Leucophaea or Rhparabia maderae), oriental cockroach (Blatta orientalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; further, Orthoptera, for example the house cricket (Acheta domesticus); termites such as the eastern subterranean termite (Reticulitermes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasius niger); and the like,

The Diptera contemplated herein comprise essentially the flies, such as the vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly (Ceratitis capitata), the house fly (Musca domestica), the little house fly (Farmia canicularis), the black blow fly (Phormia regina) and bluebottle fly (Calliphor'a erythrocephala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi); and the like.

With the mites (Acarina) contemplated herein there are classed, in particular, the spider mites (Tetranychidae) such as the two-spotted spider mite (Tetranychus telarius Tetranychus althaea or Tetranychus urticae) and the European red mite (Paratetranychus pilosus Panonychus ulmi), gall mites, for example the black currant gall mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitarsonemus latus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Ornithodorus moubata); and the like.

When applied against pests harmful to health and pests of stored products, particularly flies and mosquitoes, the compounds of this invention are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspension, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents 'and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purposeP aerosol propellants which are gaseous at normal temperatures and pressures, such as freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), paraffins (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.) sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other acaricides, insecticides and fungicides or bactericides, nematocides, rodenticides, herbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use. As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1 and 95% by weight, and preferably 05-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001 and preferably 0.0ll%, by weight of the mixture.

Thus, the present invention contemplates over-all compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and- /or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001 and and preferably 0.0195%, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 15 to 1000 g/hectare, preferably 40 to 600 g/hectare, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight of the active compound or even the active substance alone, e.g. about 20100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects and acarids, which comprises applying to at least one of (a) such insects, (b) such acarids, and (c) the corresponding habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. an insecticidally or acaricidally, effective amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, and the like.

It will be realized, of course, than the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without-limitation, by the following examples.

EXAMPLE 1 LT, test for Diptera Test insects: Musca domestica Solvent: acetone 2 parts by weight of active compound are dissolved in 1000 parts by volume of solvent. The solution so obtained is diluted with further solvent to the desired lower concentrations.

2.5 ml of the solution of active compound are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used.

7 About 25 test insects are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test insects is periodically observed. The time which is necessary for a 100% destruction is determined.

The test insects, the active compounds, the concentrations of the active compounds and the periods of time at which there is a 100% destruction can be seen from the following Table 1.

Table 1 (LT test for Diptera) Concentration ofactive compound in the solution Active compound in LT s 0.2 60' (A) C=N-OP(OC,H5), 0.04 90' 0.008 8" CN (known) CN 0.2 30' (1 (C,H,O)2PO-N=C 0.04 75' 0.008 120' CN 0.2 30' (2) (C,H,0)2P-0N=C 0.04 60' 0.008 180' 5cm,

CN 0.2 30' H I 0.04 30' 3) (CH,0)2P0N=C 0.008 75' 0.0016 4" sc,1-1

CN I] 0.2 30' (4) (cH,o),P-o-N=c 0.04 45' 0.008 180' SC,H,-i

CN l 0.2 30'- (s) (CH30),PO-N=C 0.04 45' 0.008 210' SC H n c,i-1,0 5 CN 0.2 30' H 0.04 30' (6) PO-N=C 0.00s 75' 0.0016 4" 0,11 sci-1 1C H,O 5 CN 0.2 30' 7 P-N=C 0.04 75' 0.008 210' CH SC H -n c.11 0 5 CN 0.2 30' (a) PO-N=C 0.04 60' 0.008 150' 2": SC H,n

c,H,0 5 CN 0.2 30' 0.04 60 (9) PON=C 0.00s 90' 0.0016 s" z s SCgHr-i c,u,o 5 CN 0.2 30' 10) PON=C 0.04 60 0.008 105' C1; 5C2:

EXAMPLE 2 LT test for Diptera Test insects: Aedes aegypti Solvent: acetone 2 parts by weight of active compound are dissolved in 1000 parts by volume of solvent. The solution so obtained is diluted with further solvent to the desired lower concentrations.

2.5 ml of the solution of active compound are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. About 25 test insects are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test insects is periodically observed. The time which is necessary for a destruction is determined.

The test insects, the active compounds, the concentrations of the active compounds and the periods of time at which there is a 100% destruction can be seen from the following Table 2.

Table 2 (LT test for Diptera) Concentration of active compound of the solution Active compound in LT,

S 0.2 60' 0.04 75' (A) =N-O-P(OC H5) 0.008 T 0.0016 5" CN (known) CN 0.2 30' H 0.04 30' (l) (C H O),P-ON=C 0.008 60' 0.0016 SCH CN 0.2 30' I 0.04 (2) (C H -,O) PO-N=C 0.008 75' 0.0016 210' SC H 0.0016 210' 0.2 30 CN 0.04 30 I] 0.008 60' (3) (CH -,O) P-ON=C 0.00l6 120' 0.00032 SC,H

0.2 30' CN 0.04 30' I 0.002 60' (4) (Cl-I O) PON=C 0.0016 105' 0.00032 6" SC H-,i

0.2 30' C H O S CN 0.04 45' 0.00s 45' (6) PON=C 0.0016 90' 0.00032 5" C H SCH;

0.2 30' C H O S CN 0.04 30 0.00s 75' (I0) PON= 0.0016 105' 0.00032 210 C H,i SC H Table .2-continued (LT test for Diptera) Concentration of active v compound of the solution Active compound in LT CgHgO S CN 0.2 I 30' 0.04 45' (9) P--O--N=C 0.008 75' 0.00 l 6 l 80' cm. SC l-l --i iC;H-,O S CN' 0.2 30' I; 0.04 30' (7) O-N=C 0.008 60' 0.00 l 6 150' 0.0016 150' CH; SC;,H-,n

EXAMPLE 3 LT test for cockroaches,

Test insects: Blatta orieritalis (females) Solvent: acetone 2 parts by weight of active compound are dissolved in 1000 parts by volume of solvent. The solution so obtained is diluted with further solvent to the desired lower concentrations. I

2.5 ml of the solution of active compound are pipetted into a Petri dish. On the bottom of the Petri dish there is a filter paper witha diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compound per square meter of filter paper varies with the concentration of the solution of active compound used. 10 test insects are then placed in the Petri dish and-it'is covered with a glass lid. A

The condition of the test insects is continuously. observed for up to 8 hours, and then once after24 hours. The time which is necessary for a 100% knock down effect is determined.

The test insects, the active compounds, the concentration of the active compounds and the periods of time at which there is a 100% knock down effect can be seen from the following Table 3:

LT test Test insects: Sitophilus grdnarius Solvent: actone 2 parts by weight of active compound are dissolved in 1000 parts by volume of solvent. The solution so obtained is diluted with further solvent to the desired lower concentrations.

2.5 ml of the solution of active compound are pipetted into a Petri' dish. On the'bottom of the Petri dish there is'a filter paper with a diameter of about 9.5 cm. The Petri dish remains uncovered until the solvent has completely evaporated. The amount of active compoundper square meter of filter paper varies with the concentration of the solution of active compound used. About 25 test insects are then placed in the Petri dish and it is covered with a glass lid.

The condition of the test insects is continuously observed for up to 8 hours. The time which is necessary for a knock down effect is determined.

The test insects, the active compounds, the concentrations of the active compounds and the periods of time at which there is a 100% knock down effect can be seen from the following Table 4:

Table 4 (LTM test) Concentration Active compound of active LTM compound of the solution in S I 1 ll 0.2 180 (A) C=N0P(OCH=)1 0.04 210' 0.008 8" CN (known) CN l 0.2 60' (.3) (c1-1,o),P-o-N=c 0.04 0.008 210' 5 CN II 0.2 (s (CH,O),PO-N=C 0.04 120' 0.008 4 SC l-l n CN H 0.2 105' 4) (cH,0),P-o-N=c 0.04 0.008 5" SC,H-,i

c,1-1,0 5 CN H 0.2 75 (6) P-0N=C 0.04 120' 0.00s 4" cm, SCH,

c,11,o 5 CN ii 0.2 75' (10) P0N=C 0.04 105' 0.00s 6" Cm, scar,

c,i1,o s CN l 02 90' (s) P0-N=C 0 04 150' 0008 6'- CgHs SC3H1-fl c,i1 .,o s CN ii 0.2 90' (9): PON=C 0.04 150' 0.008 210' (3,11, spam-i 1 l l 2 EXAMPLE 5 Table 5-continued V LD test (LD test for Ornithodoros moubatal Test insects: Ornithodoros moubata (3rd nymphal Concem tage) 5 Active compound tration of active De- Solvent. acetone I compound of Strum 2 parts by weight of the active compound are disthe solution tion solved in l000 parts by volume of the solvent. The solum tion so obtained is diluted with further solvent to the 1-1 0 5| CN i0 0.2 100 desired concentrations. i 0'04 80 2.5 ml of the solution of the active compound are p1- petted into a Petri dish. On the bottom of the Petri dish C2: there is a filter paper with a diameter of about 9.5 cm. CHSO CN The Petri dish remains uncovered until the solvent has fi 0.2 100 completely evaporated. The amount of active com- P O N=C 80 pound per square meter of filter paper varies with the 0,, SC2H5 concentration of the solution of active compound used. C H o S CN 10 test insects are then placed in the Petri dish and it is 2 5 u 0,2 [00 covered with a glass lid. (8) P-O-N=C 0.04 100 The condition of the test insects is observed 3 days C2": SC3H1 it after the commencement of the experiemnts. the destruction is determined as a percentage. 02 100 The active compounds, the concentrations of the ac- (7) i -0N=C 0:04 60 tive compounds, the test insects and the results can be SC H seen from the following Table 5. C a a n Table 5 (LDM test for Ornithodoros moubata) Concen- Active compound tration 3O EXAMPLE 6 of active Decompound of structhe solution tion Drosophila test Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether H To produce a suitable preparation of active com- (A) C=No--P(0C,H,) 0.2 60 pound, 1 part by weight of the active compound is N mixed with the stated amount of solvent containing the (known) stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration. H 0 2 100 1 cc of the preparation of theactive compound is ap- (l) (C,H,O),PO-N=C 0.04 100 plied with a pipette to a filter paper disc-of 7 cm diameter. The wet disc is placed in a glass vessel containing SCH; v

vinegar flies (Drosophrla melanogqster). and covered CN 0 2 100 with a glass plate. (2) (C:H5O)L O N=C 45 After the specified periods of time., the destruction is determined as a percentage: means that all the flies are killed; 0% means that none of the flies are CN killed. 3 (H) (C H o) I o N=C g-3 :88 The active compounds, their concentrations, the 2 50 evaluation times and the degree of destruction can be SC;H -n seen from Table 6.

Table 6 (Drosophila test) Active compound Concentration of Degree of active compound destruction in in after 1 day 5 CN 0.1 100 (C) (C H O),P-ON=O SCH 0.01 100 0.001 0 (known) S CN ll 0.1 100 (3) (CH,0),P-0-N=C 0.01 100 0.001 100 Table S-continued (Drosophila test) Active compound Concentration of Degree of active compound destruction in% in%after lday CN fi 0.1 100 (4) (CH3O),PON=C 0.01 100 0.001 100 sc n;

0.1 100 (5) (c1-1,o),P-0-N=c 0.01 100 0.001 90 sc n,

0.1 100 1) (CZH5O),PON=C 0.01 100 0.001 75 scH cm o 5 CN \I] 0.1 100 (6) PN=C 0.01 100 0.001 65 cm sci-1 s CN ll 0.1 100 2) (C,H50),PON=C 0.01 100 0.001 as sc u CZHSO s CN 0.1 100 P0N=C 0.01 100 0.001 czus scar,

s CN 0.1 100 (12) (CH5O),P-0-N=C 0.01 100 0.001 100 SC H i c,1-1 .,0 s CN l 0.1 100 (9) PON=C 0.01 100 0.001 98 cm sc,11,i

s CN u 0.1 100 (11) (C2H,O), O-N=C 0.01 100 0.001

0.1 s P ON=C 0.01 100 0.001 100 G 14, scan1 ic,H,0 s CN II 0.1 100 7) PON=C 0.01 100 0.001 99 CHa $0,111

EXAMPLE 7 Bean plants (Phaseolus vulgaris), which have a height of approximately 10-30 cm., are sprayed with the preparation of the active compound until dripping wet. These bean plants are heavily infested with spider mites (Tetranychus urticae) in all stages of development.

After the specified periods of time, the effectiveness of the preparation of active compound is determined by counting the dead mites. The degree of destruction thus obtained is expressed as a percentage: 100% means that all the spider mites are killed whereas 0% means that none of the spider mites are killed.

Table 7 16 stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which have been (Tetranychus test) Active compounds Concentration of Degree of active compound destruction in in after 2 days (A) I C N O ILOCH) 0] [0O (known) S CN u I 0.1 100 (C) (CgH50)z -ON=C SCI-l 0.01 0

(known) iC;,H-,O S CN \&1 0.1 100 (7) ON=C 0.01 90 CH; a 1

heavil infested with eacha hids (M zus ersicae)are EXAMPLE 8 y P p y p Myzus test (contact action) Solvent: 3 parts by weight acetone 30 Emulsifier: 1 part by weight alkylarylpolyglycol ether sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, thedegree of destruction is determined as a percentage: 100% means that all the aphids are killed whereas 0% means that none of the aphids are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 8.

Table 8 (Myzus test) Active compound Concentration of Degree of active compound destruction in in after 1 day s N l] 0.1 100 (c) (0,11 0 ),PON SCH, 0.01 40 Table 8-continued (Myzus test) Active compound Concentration of Degree of active compound destruction in in after 1 day S CN u 0.1 100 (12) (cg-1 -O-N=C\ 0.01 99 sen-1,1

c mo CN 0.1 100 (9) -ON=C 0.01 100 ,11, sc r-1,1

CN L 0.1 100 (11) (C,H,0) ON=C 0.01 100 0.001 50 SC3H-,

z s S CN I 0.1 100 (8) P0N=C 0.01 100 CgH5 a 1 iC,H,O CN

0.1 100 (7) ON= c 0.01 100 CH; a r

The process of the present invention is illustrated in 5 v and y the following Preparative p Constitution Physical properties (refractive index, EXAMPLE 9 melting point).

CN /CN (Ila) HON=C\ 56C "b SCH (a) C1H5S CNOH I 3 (He) HON=C\ n l.5l28 To 62 g (1 mole) of ethylmercaptan in 300 cc of ace. tonitrile 1 mole of sodium methylate is added, with 40 /CN 22 cooling, and 76 g of chloroacetonitrile are subse- (I'd) H L595 quently added at 10 to 15C. Stirring is afterwards ef- 1 fected for 1 hour at room temperature l mole of so- 4 5 CN dium methyla te is again added followed by oximation (b) u (2) at 0 to 5C w1th 80 g of ethyl n1tr1te. After two days of stirring at room temperature, the liquid is distilled off Constitution scm,

To 39 g (0.3 mole) of l-cyano-l-ethylmercaptoformaldoxime (Compound ll b) in 300 cc of acetonitrile and 45 g of potassium carbonate there are added 57 g of 0,0-di-ethylthionophosphoric acid ester chloride; the temperature is effected over night, followed by pouring into 300 cc of water and extraction with 400 cc of benzene. The benzene phase is washed, dried, and the solvent is distilled off. The residue is purified by socalled slight distillation. There are so obtained 69 g (81% of theory) of the desired 0,0-diethyl-O-(lcyano-1-ethylmercaptoformaldoxime)-thionophosphoric acid ester of the refractive index n 1.5058. Analogously, the following compounds are prepared:

Refractive index Yield sci-1,

RO S CN in which R and R each is an alkyl radical with 1-6 carbon atoms, and R is an alkyl or alkoxy radical with l-6 carbon atoms. 2. Compounds according to claim 1, in which R and R each is an alkyl radical of 1-4 carbon atoms, and R, is an alkyl or alkoxy radical of l-4 carbon atoms.

3. The compound according to claim 1 wherein such compound is 0,0-dimethyl-O-( Fcyanol -ethylmercaptoformaldoxime )-thiono-phosphoric acid ester of the formula S CN 4. The compound according to claim 1 wherein such compound is 0,0-diethyl-O-( l-cyano-l -propylmercaptoformaldoxime )-thiono-phosphoric acid ester of the formula 5. The compound according to claim 1 wherein such compound is O-ethyl-O-( l-cyano-l-propylmercap- 21 22 toformaldoxime)-ethane-thiono-phosphonic acid ester iC,H-,0\ fi CN of the formula Cl-L SC;,H-,n.

C,H,O S CN 5 il 7. The compound according to claim 1 wherein such compound is O-ethyl-O-( l-cyano-l-methylmercap- Scam-n toformaldoxime)-ethane-thiono-phosphonic acid ester of the formula 6. The compound according to claim 1 wherein such C H 0 CN compound is O-isopropyl-O-( l-cyano-l-propylmercap- 5 toformaldoxime)-methane-thiono-phosphonic acid P0N=C ester of the formula C,H SCH, 

1. THIONOPHOSPHORIC(PHOSPHONIC) ACID ESTER FORMALDOXIMES OF THE GENERAL FORMULA
 2. Compounds according to claim 1, in which R and R2 each is an alkyl radical of 1-4 carbon atoms, and R1 is an alkyl or alkoxy radical of 1-4 carbon atoms.
 3. The compound according to claim 1 wherein such compound is O, O-dimethyl-O-(1-cyano-1-ethylmercaptoformaldoxime)-thiono-phosphoric acid ester of the formula
 4. The compound according to claim 1 wherein such compound is O, O-diethyl-O-(1-cyano-1-propylmercaptoformaldoxime)-thiono-phosphoric acid ester of the formula
 5. The compound according to claim 1 wherein such compound is O-ethyl-O-(1-cyano-1-propylmercaptoformaldoxime)-ethane-thiono-phosphonic acid ester of the formula
 6. The compound according to claim 1 wherein such compound is O-isopropyl-O-(1-cyano-1-propylmercaptoformaldoxime)-methane-thiono -phosphonic acid ester of the formula
 7. The compound according to claim 1 wherein such compound is O-ethyl-O-(1-cyano-1-methylmercaptoformaldoxime)-ethane-thiono-phosphonic acid ester of the formula 